Isocyanates and process of preparing same



same.

Jalpha propyl meta methylstyrene,

"Patented Oct. 7, 1958 ISOCYANATES AND PROCESS OF PREPARING SAME 8Claims. (Cl. 260-453) This invention relates to a novel class ofisocyanato isocyanatophenyl indans and to the process of preparing theMore particularly, this invention relates to isocyanato isocyanatophenylindans and isothiocyanato isothiocyanatophenyl indans and to the processof preparing the same. Still further, this invention relates to polymersof isocyanato isocyanatophenyl indans and tothe process of preparing thesame.

One of the objects of the present invention is to produce an isocyanatoisocyanatophenyl indan by reacting a phosgene with an amino aminophenylindan. A further object of the present invention is to produce polymersof "isocyanato isocyanatophenyl indans by reacting said indans withcompounds containing a plurality of reactive hydrogen atoms such aspolyhydr'ic alcohols, polyamines, polyphenols and the like. These andother objects of the present invention will be discussed ingreaterdetail hereinbelow.

The isocyanato isocyanatophenyl indans of the present invention areprepared by reacting a phosgene such as phosgene per se or thiophosgenewith an amino aminophenyl indan. The amino aminophenyl indans areprepared by reducing the nitro nitrophenyl indans. The nitro nitrophenylindans may be prepared by reacting the dimers of an alpha substitutedstyrene with nitric acid wherein the substituent in the alpha positionis an alkyl group containing from 1 to 4 carbon atoms or a halo group.In order that the present invention may be fully understood, the methodsfor preparing each of the above substituted indans will be set forthhereinbelow starting With the dimerization of the substituted styrenesthrough the nitro derivatives, amino derivatives and finally theisocyanato derivatives.

This application is a continuation-in-part of my earlier filedapplication, having the Serial No. 414,860 filed March 8, 1954, nowabandoned.

The starting materials utilized in the preparation of the novelcompounds of the present invention are substituted styrenes having analkyl group or a halo group in the alpha position. The alkyl group inthe alpha position may be any one of methyl, ethyl, propyl, and butyl.The halo group in the alpha position may be chloro, bromo, iodo orfluoro. The ring positions may be either substituted or unsubstituted.If substituted, the substituents may be an alkyl group containingbetween 1 and 4'carbon'atoms or a halo group such as those mentionedabove or both. Representative of the class of alkyl substitutedstyrenes, which may be used in the practice of the process of thepresent invention are alpha methyl styrene, alpha ethyl styrene, alphapropyl styrene, alpha butyl styrene, alpha chloro styrene, alpha bromostyrene, alpha, ortho dimethylstyrene, alpha, meta-dimethylstyrene,alpha, para-dimethylstyrene, alpha-ethyl-orthomethylstyrene,alpha-ethyl-meta methylstyrene, alpha-ethyl-para-methylstyrene,alpha-propyl-ortho-methylstyrene,

alphapropylpara-tnethylstyrene, alpha-butyl-ortho-methylstyrene, al-

pha-butyl-meta-methylstyrene, styrene, alpha-ch10ro-meta-methylstyrene,alpha-bromopara-butylstyrene, alpha-iodo-ortho-propylstyrene,alphafiuoro-para-ethylstyrene and the like.

In order that the process for the preparationof-the dimers utilized inthe practice of the process of thepresent invention maybe morecompletely understood, the following examples are set forth in which'allparts are parts by weight unless otherwise'indicated. Theseexamples areset forth primarily for the purpose of illustration and any specificenumeration of detail contained therein should not be interpreted as alimitation on the case except as is indicated in the appende'dclaims.

DIMERIZATION OF a,p'-DlMETl-IYLSTYRENE SOO'parts of toluene cooled to 5C. are introduced into a suitable reaction vessel. To the toluene, thereis added 140 parts of a sulfuric acid. The mixture is stirred thoroughlyand maintained at' a temperature of about 0-5 C. To the cooled mixture,there is added 260 parts of c p-dimethylstyrene dissolved in 200 partsof toluene. The resulting mixture is allowed to react for /2 hour at()-5 C. and is then hydrolyzed with parts of water. The organic layer iswashed free of acidic material with water and is distilled to yield 250parts of a colorless oil having a boiling point of 142-444 C. at 0.8 mm.This oil solidifies and has a melting point of 37-38 C. uncorrected.

DIMERIZATION OF a-ETHYL-p-MFTHYLSTYRENE To 400 parts of toluene at 5 C.,there is added slowly 70 parts of 95% sulfuric acid followed by 144parts of u-ethyl-p-methylstyrene dissolved in 100 parts of toluene.

The temperature is maintained at 0 10? C. during the entire addition.The resulting mixture is allowed to react for /2 hourand then ishydrolyzed withlOO parts of water. The organic material is collected,washed free of acidic material with water and distilled to yield partsof a colorless liquid having a boiling point of 160-165 C.at1 mrn.DIMERIZATION OF u,META-DIMETHYLSTYRENE terial is collected, washed anddistilled to yield 61 parts of a colorless liquid having aboiling pointof 144-148 C. at 1 mm. pressure.

DIMERIZATION OF CRUDE a,p-DIMETHYL STY- RENE To 368 parts of tolueneat.l0 C., there is added Slowly 5O partsof anhydrous aluminum chloridefollowed by 516 parts of crude (undistilled) c p-dimethylstyrenedissolvedin 368 parts of toluene while maintaining the temperature below10 C. After a 20-minute reaction time, the mixture is hydrolyzed withwater and the organic layer is collected and dried. The organic materialis distilledto give parts of a colorless oil having a boiling point ofl38140 C. at 0.5-1 mm.

DIMERIZATION OF a,p-DIMETHYLSTYRENE A mixture of 310 parts of freshlydistilled cap-dimethylstyrene and 2 parts of p-toluene sulfonic acid areheated in a steam bath for about 16 hours and then allowed to react atroom temperature for 2 /2 months, at which time the p-toulene sulfonicacid catalyst is removedby washing the organic layer with dilute sodiumbicarbonate solution. Distillatiouof the organic layer gave 151 partsofalpha-butyl-para-methyl 3 methyl indan; indan;

' about 2 hours at reflux.

3 a-very light yellow colored oil having a boiling point of l36-140 C.at 1 mm. pressure.

By dimerizing alpha alkyl styrenes or alpha halo styrenes in a mannercomparable to the examples set forth hereinabove, one could produce thefollowing indans which may then be nitrated by reacting with nitric acidto produce nitro nitrophenyl indans: lphenyl-1,3,3- t'rimethylindan; 1phenyl 1,3 diethyl 3 methylindan; l-phenyl-l,3-dipropyl-3methyl-indan;1-pheny1-1,3- dibutyl 3 methyl indan; 1 phenyl 1,3 dichloro- 1 phenyl1,3 diiodo 3 methyl- 1-phenyl-l,3-dibromo-3-rnethyl-indan; l-phenyl-1,3-difluoro-3 -methyl-indan; 1-(4-methylphenyl) -1,3,3,6- tetramethylindan; 1 (4 methylphenyl) 1,3 diethyl- 3,6-dimethyl-indan;l-(4-methylphenyl)-l,3-dipropVl-3,6- dimethyl indan; 1 (4 methylphenyl)1,3 dibutyl- 3,6- dimethyl indan; 1 (3 methylphenyl) 1,33,5-tetramethyl-indan; 1-(3-methylphenyl)-1,3-diethyl-3,5- dirnethyl indan;1 (3 -methylphenyl) 1,3 dipropyl- 3,5-dimethyl-indan;1-(3-methylphenyl)-1,3-dibutyl-3,5- dimethyl-indan;1-(3-methylphenyl)-1,3-dichloro-3,5-dimethyl -indan; 1 (3 methylphenyl)1,3 dibromo- -3,5-dimethyl-indan and the like.

In order that the nitration of the indans be more completely understood,the following examples are set forth in which all parts are parts byweight unless otherwise indicated.

METHOD FOR THE PREPARATION OF 1-(4- METHYL 3 NITROPHENYL) l,3,3,6 TETRA-METHYL-S-NITRO-INDAN Into a suitable reaction vessel equipped with athermometer and a stirrer, there is introduced 264 parts ofl-(4-methylpheny1)-1,3,3,6-tetramethyl-indan and 750 parts ofchloroform. The charge is cooled to about to 5 C. and there is added, insmall increments while constantly stirring. 396 parts of 96% sulfuricacid and 132 parts of 70.4% nitric acid. These acids are addedseparately but concurrently. The addition of these acids is maintainedat arate of 3 parts of sulfuric per part of nitric acid. The temperaturethroughout the addition is held at 0-5 C. After theaddition iscompleted, the reaction is permitted to continue for an additional 30minutes with constant stirring at the same temperature. The stirring isthen stopped and the reaction medium separates into two layers. Thechloroform layer is neutralized with sodium bicarbonate and thechloroform solution is then concentrated. On standing, pale yellowcrystals of 1-(4-methyl3-nitrophenyl)-1,3,3,6-tetramethyl- S-nitro-indanform. The chloroform is filtered ofi and the nitro indan isrecrystallized from ethanol.

PREPARATION OF 1 (4 METHYL 3 AMINO- PHENYL) 1,3,3,6 TETRAMETHYL 5 AMINO-INDAN 70.8 parts of1-(4-methyl-3-nitrophenyl)-1,3,3,6-tetramethyl-S-nitro-indan (0.2 mol),67 parts of iron powder (reduced) and 100 parts of 50% ethanol in waterare introduced into a suitable reaction vessel equipped with stirrer,thermometer and reflux condenser. The charge is heated to the refluxtemperature whereupon 5.2 parts of concentrated hydrochloric acid in 25parts of a 50% aqueous solution ofethanol is added slowly. After theaddition of the acid solution, the charge is reacted for After this twohour heating period, sufficient alcoholic potassium hydroxide toneutralize the acid present in the charge is added and the retothe--filtrate. Light orange crystals precipitate which have a melting.point of 238-241 C. The crystalline precipitate comprising the sulfatesalt of the diamine is mixed with 200 parts of water and 100 parts of 6N- sodium hydroxide and the mixture is heated to reflux,

whereupon sufiici ent ethanol is added to give a clear solution. Thissolution is then refluxed for l hour. The

.solutionis cooled and poured into ice water, a light pink METHOD FORTHE PREPARATION OF 1-(4- METHYL 3 ISOCYANATOPHENYL) 1,3,15,6-TETRAMETHYL-S-ISOCYANATO-INDAN A solution of 40 parts of :dry toluenesaturated with phosgene at 0-3 C. is prepared and there is added theretowith constant stirring, 5 parts of 1(4-methy1-3-aminophenyl)-1,3,3,6-tetramethyl-5-amino-indan dissolved indry toluene. A fine white precipitate forms. The charge is heated to55-60 C. in /z hour, whereupon a steady stream of phosgene is passedthrough the reaction mixture. After 20 minutes, at 55-60 C., the mixtureclears to a yellowish-green solution and the mixture is then brought toreflux. Reflux starts at about 102 C. and is continued for about 2hours, whereupon the reflux temperature had risen to 109 C. The phosgenestream is then stopped and the solution refluxed for an additional 45minutes. The toluene is distilled off at atmospheric pressure. When thesolution has concentrated to about 1015 parts, the remainder isdistilled under vacuum. 3 parts of1-(4-methyl-3-isocyanatophenyl)-l,3,3,6-tetramethyl-S-isocyanato-indanis produced, which is a pale yellow viscous liquid having a boilingpointof 168 C. at 0.2 mm. of mercury. The yield is 51% of theoretical. Onstanding, the diisocyanato derivative crystallizes out and isrecrystallized from heptane giving a White crystalline material with amelting point of 77-79 C., uncorrected.

PREPARATION OF 1-(4- METHYL-3-ISOTHIOCY- ANATOPHENYL) l,3,3,6-.TETRAMETHYL 5 ISOTHIOCYANATO-INDAN The preceding example is repeatedin substantially all details except that in the place of the phosgenethere is utilized thiophosgene in equivalent amounts.

PREPARATION OF 1- (4-NITROPHENYL) -1,3,3- TRIMETHYL-6-NITRO-INDAN 176parts of 1,3,3-trimethyl-l-phenyl-indan (0.75 mol) are dissolved in 750parts of chloroform. To this solution there is added in smallincrements, 297 parts of 96% sulfuric acid and 99 parts of 70.4% nitricacid while maintaining a temperature at about 0-5" C. during theincrement addition. The reaction is permitted to continue for about 3hours at 0-5 C., after the additionof the mixture of the acids. Thechloroform layer is then separated from the acid layer and washed withwater and sodium bicarbonate until neutral. Crystallization is inducedby scratching. Upon recrystallization from isopropanol, there isproduced a pale yellow product that melts at 149.5-15 1 C.

PROCESS FOR THE PREPARATION OF l-(4-AMI-NOPHENYL)-1,3,3,-TRIMETHYL-6-AMINO-INDAN 32.6 parts of1-(4-nitrophenyl)-1,3,3-trimethyl-6-nitroindan, 33.5 parts of ironpowder (reduced) and 50 parts of a 50% aqueous solution of ethanol areintroduced into a suitable reaction vessel equipped with thermometer,stirrer and reflux condenser. The chargeis' then heated to reflux. Atreflux, there isadded 2.6 parts of concentrated hydrochloric acid in12.5 parts of a 50% aqueous solution of ethyl alcohol slowly. Reactionis continued for about 2 hours after the addition is completed at refluxtemperature. The charge is then neutralized with a slight excess ofalcoholic potassium hydroxide. The iron powder is filtered off andwashed, with ethyl alc ohol. The filtrate is made alkaline with sodiumhydroxide pellets causing the diamino indan to oil out. The resultantoil is digested several times in boiling water giving a brown gummymass. The diamino indan was crystallized from heptane. Recrystallizationfrom heptane gave a light tan product melting at 93.5-94.5 C.

PREPARATION OF 1- 4-ISOCYANATO PHENYL)1,3,3-TRIMETHYL-6-ISOCYANATO-INDAN 8 parts of1-(4-aminophenyl)-1,3,3-trimethyl-6-aminoindan are dissolved in 35 partsof dry toluene and the solution is added slowly to a solution of 24parts of phosgene in 52 parts of drytoluene at 0 C. The temperature ofthe'charge is maintained at 0-3 C. during the addition. On completion ofthe addition, the mixture is heated gradually to about 55-60 C. in about40 minutes at which time a steady stream of phosgene is fed into thesystem. When the mixture had cleared from milky white to a clear, paleyellow solution (in about 30 minutes), the temperature is increased toreflux. After about 1 hour at the reflux temperature, the phosgenestream is shut off and the reaction continued at reflux for anadditional 30 minutes. The toluene is then stripped off leaving aviscous orange syrup. The ma- PREPARATION OF 1-(4-ISOTHIOCYANATOPHEN-YL) 1,3,3 TRIMETHYL 6 ISOTHIOCYA- I NATO-INDAN The preceding example isrepeated in every essential detail except that in the place of phosgene,there is substituted an equivalent amount of thiophosgene.

In the preparation of the isocyanato isocyanoto phenyl indans, thefollowing dinitro indans may be utilized-as intermediates: 1 (4 methyl 3nitrophenyl) 1,3,3,6 tetramethyl-S-nitro-indan;1-(4-ethyl-3-nitrophenyl)-1,3,3- trimethyl 6 ethyl 5 nitro indan; l (4propyl 3- nitrophenyl) 1,3,3, trimethyl 6 propyl 5 nitro indan;1-(4-butyl-3-nitrophenyl)-1,3,3-trimethyl-6-butyl- S-nitro-indan;1-(4-chloro-3-nitrophenyl)-1,3,3-trimethyl- 6-chloro-5-nitro-indan;1-(4-bromo-3-nitrophenyl)-1,3,3,- trimethyl-6-bromo-S-nitro-indan;1-(4-nitrophenyl)-l,3,3- trimethyl-6-nitro-indan;1e(3-nitrophenyl)-1,3,3-trimethyl- S-nitro-indan;1-(2-nitrophenyl)-1,3,3-trimethyl-4-nitro-indan;l-(4-methyl-3-nitrophenyl)-1,3-diethyl-3,6-dimethyl- S-nitro-indan;1-(4-methyl-3-nitrophenyl)-l,3-dipropy1-3, 6-dimethyl-S-nitro-indan;1-(4-methyl-3-nitrophenyl)-1,3- dibutyl 3,6 dimethyl 5 nitro-indan; 1 (4methyl 3 nitrophenyl) 1,3 dichloro 3,6 dimethyl 5 nitro-indan;l-(4-methyl-3-nitrophenyl)-1,3-diiodo-3,6-dimethyl-S-nitro-indan, andthe like.

Amongst diamino indans which may be used to prepare the diisocyanatoindans of the present invention are the following:l-(4-methyl-3-aminophenyl)-1,3,3,6-tetramethyl-5amino-indan; 1-(4-ethyl-3-aminophenyl) -1,3,3- trimethyl 6 ethyl 5 amino indan; 1 (4propyl 3 aminophenyl) 1,3,3 trimethyl 6 propyl 5 amino-indan;1-(4-butyl-3-aminophenyl)-1,3,3-trimethyl- 6-butyl-5-amino-indan;1-(4-chloro-3-aminophenyl)-1,3,3- trimethyl-6-chloro-5-amino-indan;1-(4-bromo-3-aminophenyl) 1,3,3 trimethyl 6- bromo 5 amino indan;1-(4-aminophenyl)-1,3,3-trimethyl-6-amino-indan; 1-(3-aminophenyl)-1,3,3-trimethyl-5-amino-indan; 1-(2-aminophenyl) 1,3,3trimethyl 4 amino indan; 1 (4 methyl 3 aminophenyl) 1,3 diethyl3,6-dimethyl 5 amino-indan; 1 (4 methyl 3 aminophenyl) 1,3dipropyl-3,6-dimethyl-S-amino-indan;1-(4-methyl-3-aminophenyl)-1,3-dibutyl-3,6-dimethyl-S-aminodndan; 1-(4-methyl 3 aminophenyl) 1,3 dichloro 3,6 dimethyl-S-amino-indan;1-(4-methyl-3-aminophenyl)-1,3-

diido-3,G-dimethyl-S-aminoindan, and the like.

Amongst the diisocyanato indans which may be prepared in accordance withthe present invention are the 61-(4-methyl-3-isocyanatophenyl)-1,3,3,6-tetra methyl-5-isocyanato-indan;1-(4-ethyl-3-isocyanatophenyl)-1,3,3-trimethyl-6-ethyl-5-isocyanato-indan;1-(4-pro pyl 3 isocyanatophenyl) 1,3,3 trimethyl 6 propyl-5-isocyanato-indan; 1-(4-butyl-3-isocyanatophenyl)-1,3,3-trimethyl-6-butyl-5-isocyanato-indan; 1-(4-chloro-3-isocyanatophenyl)1,3,3 trimethyl 6 chloro 5 isocyanato-indan;1-(4-bromo-3-isocyanatophenyl)-1,3,3-trimethyl-6-bromo-S-isocyanato-indan;1-(4-isocyanatophenyl)-1 ,3 ,3-trirnethyl-6-isocyanato-indan;l-(3-isocyanatophenyl) l,3,3trimethyl-5-isocyanato-indan; 1(2-isocyanatophenyD-1,3,3-trimethyl-4-isocyanato-indan; 1-(4-methyl 3isocyanatophenyl) 1,3 diethyl 3,6 dimethyl- 5-isocyanato-indan;1-(4-methy1-3-isocyanatophenyl)-1,3-dipropyl-3,6-dimethyl-S-isocyanato-indan; isocyanatophenyl) 1,3 dibutyl3,6 dimethyl 5 isocyanato-indan;l-(4-methyl-3-isocyanatophenyl)-1,3-dichloro-3,6-dimethyl-S-isocyanato-indan;1-(4-methyl-3-isocyanatophenyl) 1,3 diiodo 3,6 dimethyl 5isocyanato-indan; 1-(4-n1ethyl-3-isothiocyanatophenyl)-1,3,3,6-tetramethyl-5-isothiocyanato-indan; 1-(4-ethyl-3-isothiocyanatophenyl)1,3,3 trimethyl 6 ethyl 5 isothiocyanato-indan;1-(4-propyl-3-isothiocyanatophenyl)- 1,3,3-trimethyl-6-propyl-5-isothiocyanato-indan; l-(4- butyl 3isothiocyanatophenyl) 1,3,3 trimethyl 6- butyl-S-isothiocyanato-indan;1-(4-chloro-3-isothiocyanatophenyl) 1,3,3 trimethyl 6 chloro 5isothiocyanato indan; 1 (4 bromo 3 isothiocyanatophenyl) 1,3,3 trimethyl6 bromo 5 isothiocyanatoindan; 1 (4 isothiocyanatophenyl) 1,3,3trimethyl- 6 isothiocyanato indan; 1 (3 isothiocyanatophenyl)-1,3,3-trimethy1-5-isothiocyanato-indan;1-(2-isothiocyanatophenyD-1,3,3-trimethyl-4-isothiocyanato-indan; 1-(4-methyl 3 isothiocyanatophenyl) 1,3 diethyl 3,6-dimethyl-S-isothiocyanato-indan; 1-(4-methyl-3-isothiocyanatophenyl) 1,3dipropyl 3,6 dimethyl 5 isothiocyanato-indan;1-(4-methyl-3-isothiocyanato)-1,3-dibutyl-3,6-dimethyl-S-isothiocyanato-indan;1-(4-methyl-3- isothiocyanatophenyl) 1,3 dichloro 3,6 dimethyl 5-isothiocyanato-indan;l-(4-methyl-3-isothiocyanatophenyl)-1,3-diiodo-3,6-dimethyl-S-isothiocyanato-indan,and the like.

The diisocyanato indans and the diisothiocyanato indans of the presentinvention Will be found to be exceedingly useful in a'plurality ofapplications. For instance, these cyanato indans may be used in resinouscompositions such as unsaturated polyester resinous compositions where afoamed resinous material is desired. These unsaturated polyesterresinous compositions are illustrated in considerable detail in the U.S. Patents 2,255,313, 2,409,633, 2,443,735-41, inclusive, and 2,510,503.Additionally, the diisocyanato and diisothiocyanato indans of thepresent invention may be utilized in coreaction with alcohols such aspolyhydric alcohols; amines, such as following:

' polyamines, phenols, such as polyphenols and polycarboxylic acids toform resinous materials. These resinous materials may be used for theproduction of coating compositions, laminating compositions, moldingcompositions, castings, adhesives and the like.

Among the polyhydric alcohols which may be reacted with the isocyanatoindans of the present invention are ethylene glycol, 'diethylene glycol,trimethylene glycol, tetramethylene glycol, trimethylol ethane,trimethylol propane, glycerol, pinacol, arabitol, Xylitol, adonitol,mannitol, sorbitol, pentaerythritol, dipentaerythritol or any polyhydricalcohols shown in my copending application.

having the Serial No. 489,793, filed February 21, 1955,, and the like.In reacting with these diisocyanato indans,. these polyhydric alcoholsmay be used either singly or in, combination with one another.

Among the polyamines which may be used to form: resinous materials byreacting with the diisocyanato in dans of the present invention areethylene diamine, diethylene triamine, triethylene tetramine,tetraethylene pentamine, 3,3-iminobispropylamine, tris- (3-aminopro.-

1-(4-methy1-3- pyl) amine, N,N-(2-hydroxyethyl-2'-aminoethyl)amine,N,N-(3-hydroxypropyl-3'-arninopropyl) amine, or any of the diaminoindans shown hereinabove.

Among the diphenols that may be used to form resinous materials byreaction with the dicyandiamide indans of the present invention arep,p-dihydroxy diphenyl dimethyl methane, p,p'-dihydroxybenzophenone,p,p'-dihydroxy diphenyl or any of the diphenols shown in my copendingapplication having the Serial No. 443,971, filed July 16, 1954, nowUnited States Patent No. 2,754,285. These diphenols may be used eithersingly or in r11: nation with one another.

In the preparation of the diisocyanato indans of the present invention,one should react more than two mols of phosgene or thiophosgene per molof diamino indan. This reaction may be carried out over a rather wideage of temperatures such as between about -4(1 C. 3.11;: reflux.Ordinarily, it is preferred that the reaction be carried out in thepresence of an inert organic solvent such as benzene, toluene, xylene,kerosene, dichlorobenzene or mineral spirits such as Varsol No. 1,Varsol No. 2 and the like. For best yields, it is preferred to carry outthe reaction at a relatively low temperature such as between about C.and +10 C. during the initial portion of the reaction while insuringthat an excess amount of phosgene or thiophosgene is present in thesphere of reaction. The temperature may then be increased graduallywhile continuing to pass the phosgene gas through the system and finallyheating at reflux temperatures to complete the reaction. When thereaction is completed, the solvent is distilled oil and the residue maybe washed, crystallized and even recrystallized to produce a purediisocyanato derivative. The reaction may be carried out eitherbatch-wise or by continuous operation and in the latter instance, itwill be possible to recycle materials such as the phosgene. If desired,one can form the hydrochloride salt of the diamino indan and said saltcan be reacted with the phosgene or thiophosgene to produce thediisocyanato derivative.

In order to illustrate the preparation of resinous materials using theisocyanato indan of the present invention, the following examples areset forth in which all parts are parts by weight. These examples are setforth primarily for the purpose of illustration and any specificenumeration of detail contained therein should not be interpreted as alimitation on the case except as is indicated in the appended claims.

Example 1 Into a suitable reaction vessel equipped with thermometer, andstirrer, there is introduced 60.5 parts of 1-(4- isocyanatophenyl)1,3,3-trimethyl-6-isocyanato-indan dissolved in 1,000 parts of heptane andthere is added thereto, in small increments, 12.9 parts of trimethylenediamine. Exothermic reaction occurs with immediate formation of a whiteprecipitate, which had the following properties: Softening point: 210C.; melting point: 230- 240" C.

Example 2 Into a suitable reaction vessel equipped with thermometer,stirrer and refiux condenser, there is introduced 31.8 parts of1-(4-isocyanatophenyl)-1,3,3-trimethyl-6-isocyanato-indan in 1200 partsof heptane. There is added thereto 6.2 parts of ethylene glycol. Thereactants are heated gradually to reflux and held at that temperaturefor about 5 minutes. A light brown precipitate forms which has asoftening point of 165 C.

Example 3 31.8 parts of 1-(4-isocyanatophenyl)-1,3,3-trimethyl-6-isocyanato-indan in 600 parts of methyl ethyl ketone are introducedinto a suitable reaction vessel equipped with thermometer, stirrer andreflux condenser. There is added thereto 14.6 parts of adipic acid. Thecharge is heated gradually to the reflux temperature and held at thattemperature for about 10 minutes. The solvent is then stripped ofi. Oncooling, a crystalline material is produced which melts at 145--160C. toa viscous melt and remained a viscous melt with some decomposition up to280 C.

Example 4 34.6 parts of 1-(4-methyl-3-isocyanatophenyl)-1,3,3,6-tetramethyl-S-isocyanato-indan are dissolved in parts of heptane. 7.4parts of trimethylene diamine are added. The polyurea which formsprecipitates from solution as a white powderous material.

Example 5 34.6 parts of 1-(4-rnethyl-3-isocyanatophenyl)-1,3,3,6-tetramethyl-5-isocyanatoindan are dissolved in 100 parts of heptane. 6.2parts of ethylene glycol are added. The polyurethane, which forms,precipitates from solution on standing.

Example 6 100 parts of polyethylene adipate (hydroxyl number equals 50)are heated to C., whereupon 10 parts of 1- (4-methyl3-isocyanatophenyl)1,3 ,3 ,6-tetramethyl-5- isocyanato-indan are added. The reactionmixture is heated for 20 minutes at l10-120 C. At the end of thereaction time, 1 part of tolylene diamine is added. The viscosityincreases almost to a gel. The product is cured by heating the mass for1 hour at C. The resultant product is a tough, rubbery sheet.

Generally speaking, the diisocyanato indans of the present invention,including the dithiocyanato indans, may be reacted with any compoundcontaining an active hydrogen atom which includes compounds which arecapable of substitution by a metal. For polymeric purposes, thesecompounds should contain at least two active hydrogen atoms. In additionto those set forth hereinabove, there is included such compounds aswater, amides, anhydrides, ammonia, Grignard reagents, and the like.

The isocyanato indans of the present invention are best represented bythe following structural formula:

XCN (IJHQ C CH;

NCX

wherein R and R are members selected from the group consisting of H, analkyl group containing 1 to 4 carbon atoms, and a halo group, R and Rare members selected from the group consisting of an alkyl groupcontaining 1 to 4 carbon atoms, and a halo group, and X is a memberselected from the group consisting of S and O.

I claim:

wherein R and R are members selected from the group consisting of H, analkyl group containing 1 to 4 carbon atoms, and a halo group, R and Rare members selected from the group consisting of an alkyl groupcontaining 1 to 4 carbon atoms, and a halo group, and X is a memberselected from the group consisting of S and O.

wherein R and R are members selected from the group consisting of H, analkyl group containing 1 to 4 carbon atoms, an a halo group, and R and Rare members selected from the group consisting of an alkyl groupcontaining 1 to 4 carbon atoms, and a halo group.

SON CHI NOS wherein R and R are members selected from the groupconsisting of H, an alkyl group containing 1 to 4 carbon atoms, and ahalo group, and R and R are members selected from the group consistingof an alkyl group containing 1 to 4 carbon atoms, and a halo group.

wherein X is a member selected from the group consisting of S and O. Y

7. 1- 3-isocyanatophenyl-1,3,3,-trimethyl-5-isocyanatoindan.

8. 1-(3-isothiocyanatopheny1)-1,3,3-trimethyl-5-isothiocyanato-indan.

References Cited in the file of this patent UNITED STATES PATENTS2,292,443 Hanford Aug. 11, 1942 2,680,129 Flores June 1, 1954 2,692,275Bortnick Oct. 19, 1954 OTHER REFERENCES An Outline of Organic NitrogenCompounds, Degering (1945), pp. 543 (paragraph 1725) and 548 (paragraph1745).

